CN106856241B - Multiphase composite nano-structure cathode material and preparation method thereof - Google Patents

Multiphase composite nano-structure cathode material and preparation method thereof Download PDF

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CN106856241B
CN106856241B CN201611244053.3A CN201611244053A CN106856241B CN 106856241 B CN106856241 B CN 106856241B CN 201611244053 A CN201611244053 A CN 201611244053A CN 106856241 B CN106856241 B CN 106856241B
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黄镇东
马延文
张坤
冯晓苗
刘瑞卿
李盼
林秀婧
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Nanjing University of Posts and Telecommunications
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract

The inventionDiscloses a multiphase composite nano-structure cathode material and a preparation method thereof, belonging to the field of lithium ion battery cathode materials and preparation methods thereof. The multiphase composite nano-structure cathode material is of a concrete-like structure, and nano-silicon particles modified by a surfactant are used as SiO2Source of organic titanium compound as TiO2The source is prepared by taking graphene oxide dispersion liquid as a dispersing agent and a precipitating agent, taking glucose, sucrose or polyvinylpyrrolidone as an organic carbon source and then carrying out hydrothermal reaction once2/TiO2the/graphene/C multiphase composite concrete-like nano-structure cathode material. The material can effectively overcome the defects of poor cycle stability and poor rate performance of a silicon-based negative electrode material, the ion battery prepared as the negative electrode has the advantages of high capacity and long service life, and meanwhile, the preparation method is simple and convenient and is suitable for industrial preparation, the raw materials are cheap and easy to obtain, and the material has great industrial application value.

Description

Multiphase composite nano-structure cathode material and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion battery cathode materials and preparation methods thereof, and particularly relates to a multiphase composite nano-structure cathode material and a preparation method thereof.
Background
With the rapid depletion of fossil energy sources such as petroleum, natural gas and the like, the exploitation of a large amount of shale gas also brings huge impact on the atmosphere and marine environment of the earth, so that environment-friendly new energy technologies such as solar energy, wind energy, biomass energy, tidal energy and the like are in great concern in the current human society. However, the generated energy of solar energy, wind energy and tidal energy varies with the variation of the power generation environment, and is extremely unstable, so that the generated energy cannot enter thousands of households and enterprises and public institutions through the national public power supply network, and finally a large number of new energy power plants and related equipment and material manufacturers are damaged or even shut down. How to solve the key problem, successfully peak-shaving and grid-connecting new energy power in a stable, cheap, convenient and quick manner and applying the new energy power to mobile electronic equipment, electric transportation tools and the like is always the focus of hot spots and research concerned in science and industry. The lithium ion battery has the characteristics of high volume energy density, high power density, safety, low cost, environmental friendliness and the like, is regarded as a high-performance green energy storage device, can effectively solve the grid-connected use problem of the new energy, and promotes the development and application of electric vehicles and high-performance mobile electronic equipment.
The anode material and the cathode material of the lithium ion battery are important components of the battery, and the actual capacity, the multiplying power and the stacking density of the electrode material always restrict the power and the energy density of the lithium ion battery. With the development of high-capacity energy storage devices and power lithium ion batteries, the market puts higher and stricter requirements on high-performance cathode materials. At present, research and application of high-performance lithium ion battery cathode materials mainly focus on tin (Sn), silicon (Si) and oxides thereof, and a monobasic or binary system [ (NixCoyMnz) O ] composed of nickel, cobalt, manganese and the like2]And the like. This is mainly because the above transition metals and transition metal oxides have large theoretical and practical capacities. In which Si has the highest theoretical capacity (4200 mAhg)-1) And is considered to be the most promising and currently most industrially expected negative electrode material for lithium ion batteries. However, the intrinsic defects of the silicon-based composite negative electrode material in the charging and discharging processes, namely the problems of huge volume expansion, slow ion migration rate and the like in the charging and discharging processes, greatly reduce the coulombic efficiency, energy and power density, and restrict the commercial popularization and application of the silicon-based composite negative electrode material in the fields of large-capacity batteries and large power supplies. Although some progress is made in the aspect of high-capacity silicon-based composite negative electrodes in recent years, the stacking density and the cycle stability of the silicon-based negative electrodes still cannot meet the requirements of practical application, and a larger promotion space is provided, so that the silicon-based negative electrodes become one of the key points and hot points of research of lithium battery experts.
At present, the silicon cathode material improves the cycle stability and the rate capabilityThe method is mainly realized by the following three measures, specifically as follows: (1) through the nanocrystallization of the silicon primary particles and the directional growth of the silicon nanoparticles, the migration distance of lithium ions is shortened, the multiplying power performance of the silicon cathode is improved, the decline of the electrode performance caused by the volume change in the charging and discharging process is relieved to a certain extent by utilizing the nanoscale effect, and in addition, the circulation stability of the silicon cathode can be further improved by controlling the growth direction of the silicon nanoparticles. However, the transition consideration of nanocrystallization greatly reduces the bulk density of the material and reduces the energy density of the silicon cathode; in addition, although the directional controllable preparation of the silicon nanoparticles is helpful for improving the circulation stability of the material, the preparation process is complex, the yield is low, the cost is high, and the method is not beneficial to industrial application; (2) the carbon-coated SiO can be controllably prepared by reasonably designing the microstructure of the silicon-based nano material2Or TiO2The silicon nano-particle core-shell and hollow structure coated with the silicon nano-particle is used for inhibiting the volume change of the silicon core in the charging and discharging process to a certain extent by applying a certain compressive stress to the silicon nano-particle core, and stabilizing a solid electrolyte interface phase, so that the cycling stability of the silicon nano-material is better improved; however, the preparation process of the material is complex, the efficiency is relatively low, and the cost is relatively high, so that the material and the preparation process thereof are not suitable for the requirements of future large-scale production and industrial application. (3) The carbon nano tube and the graphene are used for constructing a three-dimensional conductive network, and the space in the three-dimensional conductive network frame is used for relieving the volume change generated in the charging and discharging process, so that the silicon-carbon negative electrode material with better rate capability and cycling stability is obtained. However, at present, the prices of carbon nanotubes and graphene are still high, and the carbon nanotubes and graphene are not suitable for large-scale commercial application.
At present, the high-performance silicon-carbon cathode material is designed and prepared mainly by a multi-step method and a method of cooperating a plurality of measures. Typical examples include that firstly, the electrostatic spinning technology is utilized to prepare a carbon nano fiber hard template, then the CVD method is utilized to deposit nano silicon material on the fiber surface, and then the solution method is utilized to prepare a layer of TiO on the silicon carbon core-shell surface2Nano-layer, finally obtaining C/Si/TiO after heat treatment2A multilayer core-shell structure. The material has better rate capabilityThe material has the advantages of high cycling stability, complex preparation process, long period, high cost and low yield, so that the material is not beneficial to the commercial application of the material. Therefore, the synthesis method which is simple in development process, short in period and low in cost and suitable for commercial large-scale production for preparing the high-performance silicon-carbon anode material becomes one of the key points and hot points of research.
Disclosure of Invention
Aiming at the problems of poor cycling stability, poor rate capability, complex preparation method, low efficiency, high cost and the like of a silicon-based negative electrode material in the prior art, the invention provides a multiphase composite nano-structure negative electrode material and a preparation method thereof, wherein the multiphase composite nano-structure negative electrode material has a concrete-like structure and can solve the problems of poor cycling stability, poor rate capability, complex preparation process, high cost and the like of a high-capacity silicon-carbon negative electrode material for a lithium ion battery.
The purpose of the invention is realized by the following technical scheme.
The multiphase composite nano-structure cathode material is characterized in that the structure of the multiphase composite nano-structure cathode material is Si/SiO2/TiO2the/graphene/C multiphase composite.
The preparation method of the multiphase composite nano-structure cathode material comprises the following preparation steps:
s1 dispersing and surface treating silicon nano particles;
s2 co-modification of silicon nanoparticles;
s3 dispersion of the co-modified silicon nanoparticle suspension;
s4, adding glucose, sucrose or polyvinylpyrrolidone organic carbon source;
s5, carrying out a carbonization reduction reaction of glucose, sucrose or a polyvinylpyrrolidone organic carbon source;
and S6 low-temperature annealing.
Further, in step S1, the diameter of the silicon nanoparticles is 30-100 nm.
Further, the dispersing and surface treating steps of the silicon nanoparticles in step S1 are: weighing 1g of nano silicon powder, placing the nano silicon powder in 50-150 mL of ethanol, performing ultrasonic dispersion treatment for 15-30 min, adding 0.2-2 mL of Tetraethoxysilane (TEOS) serving as a surfactant under the condition of magnetic stirring, and performing ultrasonic dispersion for 15-30 min.
Further, the co-modification of the silicon nanoparticles in step S2 includes: and (4) dropwise adding 0.1-1 mL of tetrabutyl titanate into the TEOS surface-modified silicon nanoparticle ethanol dispersion obtained in the step S1 with the aid of magnetic stirring, and stirring at a constant speed for 0.5-1 h.
Further, the step of co-modifying the dispersion of the silicon nanoparticle suspension in step S3 is: and (4) dropwise adding the co-modified silicon nanoparticle suspension obtained in the step (S2) into 20-50 mL of Graphene Oxide (GO) dispersion liquid under the condition of uniform stirring, and continuously stirring for 0.5-3 h after the uniform stirring addition is finished.
Furthermore, the concentration of the Graphene Oxide (GO) dispersion liquid is 0.5-0.1 mg/mL.
Further, the step of adding an organic carbon source such as glucose, sucrose or polyvinylpyrrolidone in step S4 is: adding 0.05g to 0.5g of glucose, sucrose or polyvinylpyrrolidone powder into the co-modified silicon nanoparticle suspension obtained in the step S3, and stirring at a constant speed for 0.5 to 3 hours.
Further, in step S5, the step of the carbonization-reduction reaction of the organic carbon source such as glucose, sucrose or polyvinylpyrrolidone is: and (5) placing the solution obtained in the step (S4) in a hydrothermal reaction kettle, carrying out hydrothermal reaction for 2-10 h at 160-220 ℃, then washing the reaction product with water for 3 times, then washing with ethanol for three times, and drying at 80 ℃.
Furthermore, in the step S6, the annealing temperature is 350-600 ℃, and the annealing time is 2-6 h.
Compared with the prior art, the invention has the advantages that:
(1) SiO in the multiphase composite nano-structure cathode material2And TiO2The graphene and the porous carbon play a role in effectively inhibiting the volume expansion of Si, and the SiO is used as cement while the graphene and the porous carbon play a role in inhibiting the volume expansion of Si2And TiO2The coated Si nano particles are bonded together to form a three-dimensional concrete structure, so that the internal stress caused by volume change in the charging and discharging processes of the Si nano particles is buffered, and the cyclicity of the silicon nano particles is further improvedEnergy is saved;
(2) according to the invention, the multiphase composite nano-structure cathode material graphene and the porous carbon material form a three-position interconnected conductive network together, so that the multiplying power performance of the Si cathode is effectively improved;
(3) the multiphase composite nano-structure cathode material Si/SiO of the invention2/TiO2the/graphene/C multiphase composite concrete-like nano-structure cathode material has high capacity (500-1000 mAh/g) and long service life (after two cycles of charge-discharge activation, the capacity of 300 cycles is kept more than 100%);
(4) the preparation method of the multiphase composite nano-structure cathode material is simple and convenient, is suitable for industrial preparation, has cheap and easily obtained raw materials, has great industrial application value, and is one of important cathode materials of high-capacity and high-power lithium ion batteries in the future.
Drawings
FIG. 1 is a scanning electron micrograph of SSTGC-1;
FIG. 2 is an X-ray diffraction pattern of SSTGC-1 and a precursor SSTGC-1-P;
FIG. 3 is a first turn charge-discharge curve of SSTGC-1 at a current density of 0.1C;
FIG. 4 is a graph of the charge and discharge cycles of SSTGC-1 at 0.1C and 0.5C.
Detailed Description
The invention is described in detail below with reference to the drawings and specific examples.
Example 1
The invention relates to a nano composite cathode material with a concrete-like structure and a preparation method thereof, belonging to high-capacity and long-service-life power and energy storage lithium ion batteries Si/SiO2/TiO2A/graphene/C multiphase composite concrete nano-structure cathode material and a low-cost large-scale one-time preparation method thereof.
The technical scheme of the invention utilizes silicon-containing organic matter as a surfactant to modify nano silicon particles and takes an organic titanium compound as TiO2The source is prepared by taking graphene oxide dispersion liquid as a dispersing agent and a precipitating agent, taking glucose, sucrose or polyvinylpyrrolidone and the like as organic carbon sources, and performing hydrothermal reactionOne-step preparation of Si/SiO2/TiO2the/graphene/C multiphase composite concrete nano-structure cathode material. The preparation method comprises the following steps:
(1) 1g of 50 nano silicon powder is weighed and placed in 100mL of ethanol, and after 15min of ultrasonic dispersion treatment, primarily dispersed nano silicon ethanol suspension is obtained.
(2) Under the condition of uniform stirring, 2mL of Tetraethoxysilane (TEOS) is used as a surfactant and is added into the nano-silicon ethanol suspension prepared in the step 1 drop by drop, and then ultrasonic dispersion treatment is carried out for 30min to obtain the TEOS surface modified silicon nano-particle ethanol dispersion liquid.
(3) And (3) dropwise adding 0.5mL of tetrabutyl titanate into the TEOS surface-modified silicon nanoparticle ethanol dispersion liquid obtained in the step (2) under the condition of uniform stirring, and stirring at a uniform speed for 30min to obtain a co-modified silicon nanoparticle ethanol dispersion liquid.
(4) 50mL of Graphene Oxide (GO) dispersion liquid with the concentration of 1mg/mL is taken, 50mL of deionized water is added, and the graphene oxide dispersion liquid is shaken up to obtain a graphene oxide diluted solution with the concentration of 0.5 mg/mL.
(5) Dropwise adding the co-modified silicon nanoparticle suspension obtained in the step (3) into 40mL of GO dispersion obtained in the step (4) under the condition of uniform stirring, continuously stirring for 1h after the uniform stirring addition is finished, and fully hydrolyzing tetrabutyl titanate and ethyl orthosilicate to form uniform and stable Si/SiO2/TiO2Graphene oxide mixed colloid suspension dispersion liquid.
(6) 0.2g of glucose powder was added to the Si/SiO solid obtained in step 52/TiO2In the graphene oxide mixed colloid suspension dispersion liquid, continuously stirring at a constant speed for 1h to obtain Si/SiO in the mixed solvent of ethanol and water2/TiO2Graphene oxide/glucose mixed solution.
(7) And (4) placing the mixed solution obtained in the step (6) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 6h at 200 ℃. Then washing the reaction product with water for 3 times, then washing with ethanol for 3 times, and drying at 80 ℃ to obtain Si/SiO2/TiO2Reduced graphene oxide/porous carbon multiphase composite material precursor.
(8) Finally, the product obtained in the step (7)Si/SiO2/TiO2Annealing the reduced graphene oxide/porous carbon multiphase composite material precursor at the low temperature of 450 ℃ for 5h to further remove oxygen-containing functional groups in the reduced graphene and the hydrothermal porous carbon, and finally obtaining Si/SiO with excellent conductivity2/TiO2A/graphene/porous carbon (SSTGC-1) multiphase composite material, shown in FIG. 1, SiO2And TiO2The coated silicon nano particles are dispersed and distributed in a multiphase composite nano structure material which is formed by graphene and carbon and is similar to a concrete structure.
SSTGC-1 electrode preparation:
the SSTGC-1 type 'concrete' structure multiphase nano composite material (80%) shown in figure 1, conductive carbon black (10%) and a binder (PVDF, 10%) are uniformly mixed to prepare uniform slurry, the obtained colloid is coated on the surface of a copper foil, after the copper foil is dried for 3 hours at 70 ℃, the copper foil is continuously dried for 5 hours in vacuum at 90 ℃, and an SSTGC-1 electrode is finally obtained.
Assembling the button cell: lithium sheets are used as a counter electrode and a reference electrode, and 1mol/L LiPF is used6The prepared SSTGC-1 electrode is taken as a working electrode and assembled into a button type lithium ion half cell in a vacuum glove box.
Electrochemical performance characteristics: and carrying out electrochemical performance test on the assembled button cell by using a blue battery test system. Fig. 3 is a constant current charge and discharge curve of the SSTGC-1 electrode at a current density of 0.1C (1C ═ 4200mA/g), and the discharge and charge capacity of the first circle of the battery can reach 2176 and 1250mAh/g at 0.1C. Particularly, the specific capacity can still be kept at 881mAh/g and 760mAh/g after 100 cycles of charge-discharge cycle tests under the current density of 0.1C and 0.5C, respectively, as shown in FIG. 4.
Example 2
(1) 1g of 30 nano silicon powder is weighed and placed in 100mL of ethanol, and after 15min of ultrasonic dispersion treatment, primarily dispersed nano silicon ethanol suspension is obtained.
(2) Under the condition of uniform stirring, 1mL of Tetraethoxysilane (TEOS) is used as a surfactant and is added into the nano-silicon ethanol suspension prepared in the step (1) dropwise, and then ultrasonic dispersion treatment is carried out for 15min to obtain the TEOS surface modified silicon nano-particle ethanol dispersion liquid.
(3) And (3) dropwise adding 0.4mL of tetrabutyl titanate into the TEOS surface-modified silicon nanoparticle ethanol dispersion liquid obtained in the step (2) under the condition of uniform stirring, and stirring at a uniform speed for 1h to obtain co-modified silicon nanoparticle ethanol dispersion.
(4) 50mL of Graphene Oxide (GO) dispersion liquid with the concentration of 1mg/mL is taken, 50mL of deionized water is added, and the graphene oxide dispersion liquid is shaken up to obtain a graphene oxide diluted solution with the concentration of 0.5 mg/mL.
(5) Dropwise adding the co-modified silicon nanoparticle suspension obtained in the step (3) into 40mL of GO dispersion obtained in the step (4) under the condition of uniform stirring, continuously stirring for 1h after the uniform stirring addition is finished, and fully hydrolyzing tetrabutyl titanate and ethyl orthosilicate to form uniform and stable Si/SiO2/TiO2Graphene oxide mixed colloid suspension dispersion liquid.
(6) 0.4g of glucose powder was added to the Si/SiO powder obtained in step (5)2/TiO2In the graphene oxide mixed colloid suspension dispersion liquid, continuously stirring at a constant speed for 2 hours to obtain Si/SiO in the mixed solvent of ethanol and water2/TiO2Graphene oxide/glucose mixed solution.
(7) And (4) placing the mixed solution obtained in the step (6) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 10 hours at 180 ℃. Then washing the reaction product with water for 3 times, then washing with ethanol for 3 times, and drying at 80 ℃ to obtain Si/SiO2/TiO2Reduced graphene oxide/porous carbon multiphase composite material precursor.
(8) Finally, the Si/SiO obtained in the step (7)2/TiO2Annealing the reduced graphene oxide/porous carbon multiphase composite material at the low temperature of 500 ℃ for 3h to further remove oxygen-containing functional groups in the reduced graphene and the hydrothermal porous carbon, and finally obtaining Si/SiO with excellent conductivity2/TiO2The composite material comprises/graphene/porous carbon (SSTGC-2) multiphase composite material.
SSTGC-2 electrode preparation: uniformly mixing an SSTGC-2 multiphase nano composite material (80%), conductive carbon black (10%) and a binder (PVDF, 10%) to prepare uniform slurry, coating the obtained colloid on the surface of a copper foil, drying at 70 ℃ for 3h, and continuing to dry at 90 ℃ for 5h in vacuum, thereby finally obtaining the SSTGC-2 electrode.
Assembling the button cell: lithium sheets are used as a counter electrode and a reference electrode, and 1mol/L LiPF is used6The prepared SSTGC-2 electrode is a working electrode and is assembled into a button lithium ion half-cell in a vacuum glove box.
Electrochemical performance characteristics: the electrochemical performance of the assembled button cell is tested by a blue cell test system, and the specific capacity of the assembled button cell can be kept at 863mAh/g and 752mAh/g respectively after 100-circle charge-discharge cycle test under the current density of 0.1C and 0.5C (1C is 4200 mA/g). Under the current density of 0.1C, the specific discharge capacity of the first circle of the battery can reach 2150 mAh/g.
Example 3
(1) 1g of 90 nano silicon powder is weighed and placed in 100mL of ethanol, and after 15min of ultrasonic dispersion treatment, primarily dispersed nano silicon ethanol suspension is obtained.
(2) Under the condition of uniform stirring, 0.4mL of Tetraethoxysilane (TEOS) is used as a surfactant and is added into the nano-silicon ethanol suspension prepared in the step (1) drop by drop, and then ultrasonic dispersion treatment is carried out for 30min to obtain the TEOS surface modified silicon nano-particle ethanol dispersion liquid.
(3) And (3) dropwise adding 0.2mL of tetrabutyl titanate into the TEOS surface-modified silicon nanoparticle ethanol dispersion liquid obtained in the step (2) under the condition of uniform stirring, and stirring at a uniform speed for 30min to obtain a co-modified silicon nanoparticle ethanol dispersion liquid.
(4) 50mL of Graphene Oxide (GO) dispersion liquid with the concentration of 1mg/mL is taken, 200mL of deionized water is added, and the graphene oxide dispersion liquid is shaken up to obtain a graphene oxide diluted solution with the concentration of 0.2 mg/mL.
(5) Dropwise adding the co-modified silicon nanoparticle suspension obtained in the step (3) into 30mL of GO dispersion obtained in the step (4) under the condition of uniform stirring, continuously stirring for 2h after the uniform stirring addition is finished, and fully hydrolyzing tetrabutyl titanate and ethyl orthosilicate to form uniform and stable Si/SiO2/TiO2Graphene oxide mixed colloid suspension dispersion liquid.
(6) 0.1g of polyvinylpyrrolidone powder was added to the Si/SiO powder obtained in step (5)2/TiO2In the graphene oxide mixed colloid suspension dispersion liquid, continuously stirring at a constant speed for 1h to obtain Si/SiO in the mixed solvent of ethanol and water2/TiO2Graphene oxide/glucose mixed solution.
(7) And (4) placing the mixed solution obtained in the step (6) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 2h at 220 ℃. Then washing the reaction product with water for 3 times, then washing with ethanol for 3 times, and drying at 80 ℃ to obtain Si/SiO2/TiO2Reduced graphene oxide/porous carbon multiphase composite material precursor.
(8) Finally, the Si/SiO obtained in the step 72/TiO2Annealing the reduced graphene oxide/porous carbon multiphase composite material at the low temperature of 600 ℃ for 3h to further remove oxygen-containing functional groups in the reduced graphene and the hydrothermal porous carbon, and finally obtaining Si/SiO with excellent conductivity2/TiO2The composite material comprises/graphene/porous carbon (SSTGC-3) multiphase composite material.
SSTGC-3 electrode preparation: uniformly mixing an SSTGC-3 multiphase nano composite material (80%), conductive carbon black (10%) and a binder (PVDF, 10%) to prepare uniform slurry, coating the obtained colloid on the surface of a copper foil, drying at 70 ℃ for 3 hours, and continuing to dry at 90 ℃ for 5 hours in vacuum to finally obtain an SSTGC-1 electrode.
Assembling the button cell: lithium sheets are used as a counter electrode and a reference electrode, and 1mol/L LiPF is used6The prepared SSTGC-3 electrode is taken as a working electrode and is assembled into a button type lithium ion half-cell in a vacuum glove box.
Electrochemical performance characteristics: the electrochemical performance of the assembled button cell is tested by a blue cell test system, and the specific capacity of the assembled button cell can be respectively maintained at 842mAh/g and 714mAh/g after 100-circle charge-discharge cycle test under the current density of 0.1C and 0.5C (1C is 4200 mA/g). Under the current density of 0.1C, the specific discharge capacity of the first circle of the battery can reach 2205 mAh/g.
Example 4
(1) 1g of 50 nano silicon powder is weighed and placed in 100mL of ethanol, and after 15min of ultrasonic dispersion treatment, primarily dispersed nano silicon ethanol suspension is obtained.
(2) Under the condition of uniform stirring, 0.5mL of Tetraethoxysilane (TEOS) is used as a surfactant and is added into the nano-silicon ethanol suspension prepared in the step (1) drop by drop, and then ultrasonic dispersion treatment is carried out for 30min to obtain the TEOS surface modified silicon nano-particle ethanol dispersion liquid.
(3) And (3) dropwise adding 1mL of tetrabutyl titanate into the TEOS surface-modified silicon nanoparticle ethanol dispersion liquid obtained in the step (2) under the condition of uniform stirring, and stirring at a uniform speed for 1.5 hours to obtain a co-modified silicon nanoparticle ethanol dispersion liquid.
(4) 50mL of Graphene Oxide (GO) dispersion liquid with the concentration of 1mg/mL is taken, 50mL of deionized water is added, and the graphene oxide dispersion liquid is shaken up to obtain a graphene oxide diluted solution with the concentration of 0.5 mg/mL.
(5) Dropwise adding the co-modified silicon nanoparticle suspension obtained in the step (3) into 40mL of GO dispersion obtained in the step (4) under the condition of uniform stirring, continuously stirring for 1h after the uniform stirring addition is finished, and fully hydrolyzing tetrabutyl titanate and ethyl orthosilicate to form uniform and stable Si/SiO2/TiO2Graphene oxide mixed colloid suspension dispersion liquid.
(6) 0.2g of sucrose powder was added to the Si/SiO powder obtained in step (5)2/TiO2In the graphene oxide mixed colloid suspension dispersion liquid, continuously stirring at a constant speed for 1h to obtain Si/SiO in the mixed solvent of ethanol and water2/TiO2Graphene oxide/glucose mixed solution.
(7) And (4) placing the mixed solution obtained in the step (6) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 6h at 200 ℃. Then washing the reaction product with water for 3 times, then washing with ethanol for 3 times, and drying at 80 ℃ to obtain Si/SiO2/TiO2Reduced graphene oxide/porous carbon multiphase composite material precursor.
(8) Finally, the Si/SiO obtained in the step (7)2/TiO2Annealing the reduced graphene oxide/porous carbon multiphase composite material at the temperature of 450 ℃ for 5 hours to further remove oxygen-containing functional groups in the reduced graphene and the hydrothermal porous carbon, and finally obtaining Si/SiO with excellent conductivity2/TiO2The composite material comprises/graphene/porous carbon (SSTGC-4) multiphase composite material.
SSTGC-4 electrode preparation: uniformly mixing an SSTGC-4 multiphase nano composite material (80%), conductive carbon black (10%) and a binder (PVDF, 10%) to prepare uniform slurry, coating the obtained colloid on the surface of a copper foil, drying at 70 ℃ for 3h, and continuing to dry at 90 ℃ for 5h in vacuum, thereby finally obtaining the SSTGC-4 electrode.
Assembling the button cell: lithium sheets are used as a counter electrode and a reference electrode, and 1mol/L LiPF is used6The EC + DEC solution is used as electrolyte, and the SSTGC-4 electrode is used as a working electrode to assemble a button type lithium ion half cell in a vacuum glove box.
Electrochemical performance characteristics: the electrochemical performance of the assembled button cell is tested by a blue cell test system, and the specific capacity of the assembled button cell can be respectively maintained at 821mAh/g and 752mAh/g after 100-circle charge-discharge cycle test under the current density of 0.1C and 0.5C (1C is 4200 mA/g). Under the current density of 0.1C, the specific discharge capacity of the first circle of the battery can reach 2105 mAh/g.
Example 5
(1) 1g of 30 nano silicon powder is weighed and placed in 100mL of ethanol, and after 15min of ultrasonic dispersion treatment, primarily dispersed nano silicon ethanol suspension is obtained.
(2) Under the condition of uniform stirring, 0.2mL of Tetraethoxysilane (TEOS) is used as a surfactant and is added into the nano-silicon ethanol suspension prepared in the step (1) drop by drop, and then ultrasonic dispersion treatment is carried out for 30min to obtain the TEOS surface modified silicon nano-particle ethanol dispersion liquid.
(3) And (3) dropwise adding 0.1mL of tetrabutyl titanate into the TEOS surface-modified silicon nanoparticle ethanol dispersion liquid obtained in the step (2) under the condition of uniform stirring, and stirring at a uniform speed for 30min to obtain a co-modified silicon nanoparticle ethanol dispersion liquid.
(4) 50mL of Graphene Oxide (GO) dispersion liquid with the concentration of 1mg/mL is taken, 450mL of deionized water is added, and the graphene oxide dispersion liquid is shaken up to obtain a graphene oxide diluted solution with the concentration of 0.1 mg/mL.
(5) Dropwise adding the co-modified silicon nanoparticle suspension obtained in the step (3) into 40mL of GO dispersion obtained in the step (4) under the condition of uniform stirring, continuously stirring for 1h after the uniform stirring is finished, and fully hydrolyzing tetrabutyl titanate and ethyl orthosilicate to formTo form uniform and stable Si/SiO2/TiO2Graphene oxide mixed colloid suspension dispersion liquid.
(6) 0.1g of glucose powder was added to the Si/SiO powder obtained in step (5)2/TiO2In the graphene oxide mixed colloid suspension dispersion liquid, continuously stirring at a constant speed for 1h to obtain Si/SiO in the mixed solvent of ethanol and water2/TiO2Graphene oxide/glucose mixed solution.
(7) And (4) placing the mixed solution obtained in the step (6) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 160 ℃. Then washing the reaction product with water for 3 times, then washing with ethanol for 3 times, and drying at 80 ℃ to obtain Si/SiO2/TiO2Reduced graphene oxide/porous carbon multiphase composite material precursor.
(8) Finally, the Si/SiO obtained in the step (7)2/TiO2Annealing the reduced graphene oxide/porous carbon multiphase composite material at 550 ℃ for 3h to further remove oxygen-containing functional groups in the reduced graphene and the hydrothermal porous carbon, and finally obtaining Si/SiO with excellent conductivity2/TiO2The composite material comprises/graphene/porous carbon (SSTGC-5) multiphase composite material.
SSTGC-5 electrode preparation: SSTGC-5 multiphase nanocomposite (80%), conductive carbon black (10%) and a binder (PVDF, 10%) are uniformly mixed to prepare uniform slurry, the obtained colloid is coated on the surface of a copper foil, the copper foil is dried at 70 ℃ for 3 hours, and then the copper foil is continuously dried at 90 ℃ for 5 hours in vacuum, and finally an SSTGC-5 electrode is obtained.
Assembling the button cell: lithium sheets are used as a counter electrode and a reference electrode, and 1mol/L LiPF is used6The EC + DEC solution is used as electrolyte, and the SSTGC-5 electrode is used as a working electrode to assemble the button lithium ion battery in a vacuum glove box.
Electrochemical performance characteristics: the electrochemical performance of the assembled button cell is tested by a blue battery test system, and the specific capacity of the assembled button cell can be respectively maintained at 801mAh/g and 683mAh/g after 100-circle charge-discharge cycle test under the current density of 0.1C and 0.5C (1C is 4200 mA/g). Under the current density of 0.1C, the specific discharge capacity of the first ring of the battery can reach 2355 mAh/g.
Example 6
(1) 1g of 70 nano silicon powder is weighed and placed in 100mL of ethanol, and after 15min of ultrasonic dispersion treatment, primarily dispersed nano silicon ethanol suspension is obtained.
(2) Under the condition of uniform stirring, 0.5mL of Tetraethoxysilane (TEOS) is used as a surfactant and is added into the nano-silicon ethanol suspension prepared in the step (1) drop by drop, and then ultrasonic dispersion treatment is carried out for 1h to obtain the TEOS surface modified silicon nano-particle ethanol dispersion liquid.
(3) And (3) dropwise adding 1mL of tetrabutyl titanate into the TEOS surface-modified silicon nanoparticle ethanol dispersion liquid obtained in the step (2) under the condition of uniform stirring, and stirring at a uniform speed for 1h to obtain a co-modified silicon nanoparticle ethanol dispersion liquid.
(4) 50mL of Graphene Oxide (GO) dispersion liquid with the concentration of 1mg/mL is taken, 50mL of deionized water is added, and the graphene oxide dispersion liquid is shaken up to obtain a graphene oxide diluted solution with the concentration of 0.5 mg/mL.
(5) Dropwise adding the co-modified silicon nanoparticle suspension obtained in the step (3) into 40mL of GO dispersion obtained in the step (4) under the condition of uniform stirring, continuously stirring for 1h after the uniform stirring and addition are finished, and fully hydrolyzing tetrabutyl titanate and ethyl orthosilicate to form uniform and stable Si/SiO2/TiO2Graphene oxide mixed colloid suspension dispersion liquid.
(6) 0.5g of glucose powder was added to the Si/SiO powder obtained in step (5)2/TiO2In the graphene oxide mixed colloid suspension dispersion liquid, continuously stirring at a constant speed for 1.5h to obtain Si/SiO in the mixed solvent of ethanol and water2/TiO2Graphene oxide/glucose mixed solution.
(7) And (4) placing the mixed solution obtained in the step (6) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 6h at 200 ℃. Then washing the reaction product with water for 3 times, then washing with ethanol for 3 times, and drying at 80 ℃ to obtain Si/SiO2/TiO2Reduced graphene oxide/porous carbon multiphase composite material precursor.
(8) Finally, the Si/SiO obtained in the step (7)2/TiO2Annealing the reduced graphene oxide/porous carbon multiphase composite material at the low temperature of 400 ℃ for 6h to further remove the reduced graphene and hydrothermal processThe Si/SiO with excellent conductivity is finally obtained by the oxygen-containing functional group in the porous carbon2/TiO2A/graphene/porous carbon (SSTGC-6) multiphase composite material.
SSTGC-6 electrode preparation: uniformly mixing an SSTGC-1 multiphase nano composite material (80%), conductive carbon black (10%) and a binder (PVDF, 10%) to prepare uniform slurry, coating the obtained colloid on the surface of a copper foil, drying at 70 ℃ for 3h, and continuing to dry at 90 ℃ for 5h in vacuum, thereby finally obtaining the SSTGC-6 electrode.
Assembling the button cell: lithium sheets are used as a counter electrode and a reference electrode, and 1mol/L LiPF is used6The EC + DEC solution is used as electrolyte, and the SSTGC-6 electrode is used as a working electrode to assemble a button type lithium ion half cell in a vacuum glove box.
Electrochemical performance characteristics: the electrochemical performance of the assembled button cell is tested by a blue cell test system, and the specific capacity of the assembled button cell can be respectively kept at 875mAh/g and 747mAh/g after 100-circle charge-discharge cycle test under the current density of 0.1C and 0.5C (1C is 4200 mA/g). Under the current density of 0.1C, the specific discharge capacity of the first circle of the battery can reach 2143 mAh/g.
The invention and its embodiments have been described above schematically, without limitation, and the embodiments shown in the drawings are only one of the embodiments of the invention, and the actual structure is not limited thereto. Therefore, if a person skilled in the art receives the teachings of the present invention, without inventive design, a similar structure and an embodiment to the above technical solution should be covered by the protection scope of the present patent.

Claims (5)

1. A preparation method of a multiphase composite nano-structure cathode material comprises the following preparation steps:
s1 dispersing and surface treating silicon nanoparticles, wherein the diameter of the silicon nanoparticles is 30-100 nm, and the dispersing and surface treating steps of the silicon nanoparticles are as follows: weighing 1g of nano silicon powder, placing the nano silicon powder in 50-150 mL of ethanol, performing ultrasonic dispersion treatment for 15-30 min, adding 0.2-2 mL of Tetraethoxysilane (TEOS) serving as a surfactant under the condition of magnetic stirring, and performing ultrasonic dispersion for 15-30 min;
s2 co-modification of silicon nanoparticles, the co-modification of silicon nanoparticles comprises the following steps: dropwise adding 0.1-1 mL of tetrabutyl titanate into the TEOS surface-modified silicon nanoparticle ethanol dispersion obtained in the step S1 with the aid of magnetic stirring, and uniformly stirring for 0.5-1 h;
s3, dispersing the co-modified silicon nanoparticle suspension, wherein the dispersing step of the co-modified silicon nanoparticle suspension is as follows: dropwise adding the co-modified silicon nanoparticle suspension obtained in the step S2 into 20-50 mL of Graphene Oxide (GO) dispersion liquid under the condition of uniform stirring, and continuously stirring for 0.5-3 h after the uniform stirring is finished;
s4, adding glucose, sucrose or polyvinylpyrrolidone organic carbon source;
s5, carrying out a carbonization reduction reaction of glucose, sucrose or a polyvinylpyrrolidone organic carbon source;
and S6 low-temperature annealing.
2. The preparation method of the multiphase composite nanostructure anode material of claim 1, wherein the concentration of the Graphene Oxide (GO) dispersion liquid is 0.5-0.1 mg/mL.
3. The preparation method of the multiphase composite nano-structure anode material as claimed in claim 1, wherein the step of adding glucose, sucrose or polyvinylpyrrolidone organic carbon source in step S4 comprises: adding 0.05g to 0.5g of glucose, sucrose or polyvinylpyrrolidone powder into the co-modified silicon nanoparticle suspension obtained in the step S3, and stirring at a constant speed for 0.5 to 3 hours.
4. The method for preparing the multiphase composite nano-structure anode material according to claim 1, wherein the step S5 of the carbonization-reduction reaction of the glucose, sucrose or polyvinylpyrrolidone organic carbon source comprises the following steps: and (4) placing the solution obtained in the step (S4) in a hydrothermal reaction kettle, carrying out hydrothermal reaction for 2-10 h at 160-220 ℃, then washing the reaction product with water for 3 times, washing with ethanol for three times, and drying at 80 ℃.
5. The preparation method of the multiphase composite nanostructure anode material according to claim 1, wherein the annealing temperature in the step S6 is 350-600 ℃, and the annealing time is 2-6 h.
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